Surface oxide on thin films of yttrium hydride studied by neutron reflectometry

The applicability of standard methods for compositional analysis is limited for H-containing films. Neutron reflectometry is a powerful, non-destructive method that is especially suitable for these systems due to the large negative scattering length of H. In this work we demonstrate how neutron reflectometry can be used to investigate thin films of yttrium hydride. Neutron reflectometry gives a strong contrast between the film and the surface oxide layer, enabling us to estimate the oxide thickness and oxygen penetration depths. A surface oxide layer of 5-10 nm thickness was found for unprotected yttrium hydride films

Understanding the effects of Cr doping in rutile TiO₂ by DFT calculations and X-ray spectroscopy

The effects of Cr on local environment and electronic structure of rutile TiO₂ are studied combining theoretical and experimental approaches. Neutral and negatively charged substitutional Cr impurities Cr_(Ti)(0)* and Cr_(Ti)(-1)* as well as Cr-oxygen vacancy complex 2Cr_(Ti) + V₀ are studied by the density functional theory (DFT) within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) functional. Experimental results based on X-Ray absorption spectroscopy (XAS) and X-Ray photoelectron spectroscopy (XPS) performed on Cr doped TiO₂ at the Synchrotron facility were compared to the theoretical results. It is shown that the electrons of the oxygen vacancy tend to be localized at the t_(2g) states of the Cr ions in order to reach the stable oxidation state of Cr(3+)*. Effects of Cr on crystal field (CF) and structural distortions in the rutile TiO₂ cell were analyzed by the DFT calculations and XAS spectra revealing that the CF and tetragonal distortions in TiO₂ are very sensitive to the concentration of Cr

Synergetic improvement of stability and conductivity of hybrid composites formed by PEDOT:PSS and SnO nanoparticles

In this work, layered hybrid composites formed by tin oxide (SnO) nanoparticles synthesized by hydrolysis and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) have been analyzed. Prior to the composite study, both SnO and PEDOT:PSS counterparts were characterized by diverse techniques, such as X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), photoluminescence (PL), atomic force microscopy (AFM), optical absorption and Hall effect measurements. Special attention was given to the study of the stability of the polymer under laser illumination, as well as the analysis of the SnO to SnO_2 oxidation assisted by laser irradiation, for which different laser sources and neutral filters were employed. Synergetic effects were observed in the hybrid composite, as the addition of SnO nanoparticles improves the stability and electrical conductivity of the polymer, while the polymeric matrix in which the nanoparticles are embedded hinders formation of SnO_2. Finally, the Si passivation behavior of the hybrid composites was studied

Electrical and optical properties of composite PEDOT: PSS-based thin films with NiO nanoparticles

Due to the combination of low cost materials deposition and device fabrication methods as well as competitive efficiency compared to the other Si solar cell architectures, the hybrid organic-silicon solar cells have attracted attention of the scientific community. It has recently been demonstrated that spin-coated poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (hereafter PEDOT:PSS) on a silicon wafer is a promising material due to its good optical and electrical properties. However, degradation caused by atmospheric exposure and relatively poor passivation properties limits implementation of PEDOT:PSS- silicon devices. Functionalization of PEDOT:PSS by inorganic nanoparticles might provide a possible solution as was shown for TiO_2 and SnO_2 nanoparticles. In this contribution, we present our results on spincoated PEDOT:PSS thin-films with NiO nanoparticles. We show that PEDOT:PSS mixed with Triton X-100 and dimethyl sulfoxide (DMSO) or ethylene glycol (EG) form a homogenous film and passivates the Si surface with charge carrier lifetimes of 300-400 ms with good reproducibility. Time-resolved measurements revealed continuous degradation of the passivation properties in air, however saturation of the degradation at approximately 150 ms was observed in N_2 atmosphere. The influence of the NiO nanoparticles on the optical properties of PEDOT:PSS is negligible, whereas the surface passivation properties are worsened due probably to the formation of large size agglomerates exceeding thickness of PEDOT:PSS film

A new thin film photochromic material: Oxygen-containing yttrium hydride

In this work we report on photochromism in transparent thin film samples of oxygen-containing yttrium hydride. Exposure to visible and ultraviolet (UV) light at moderate intensity triggers a decrease in the optical transmission of visible and infrared (IR) light. The photo-darkening is colour-neutral. We show that the optical transmission of samples of 500 nm thickness can be reduced by up to 50% after one hour of illumination with light of moderate intensity. The reaction is reversible and samples that are left in the dark return to the initial transparent state. The relaxation time in the dark depends on the temperature of the sample and the duration of the light exposure. The photochromic reaction takes place under ambient conditions in the as-deposited state of the thin-film samples.Comment: Accepted for publication in Solar Energy Materials and Solar Cell

Experimental and Theoretical Investigation of Gadolinium Oxyhydride (GdHO) Thin Films : Optical, Photocatalytic, and Electronic Properties

Oxyhydrides of rare-earth metals (REMOHs) exhibit notable photochromic behaviors. Among these, yttrium oxyhydride (YHO) stands out for its impressive transparency and swift UV-responsive color change, positioning it as an optimal material for self-cleaning window applications. Although semiconductor photocatalysis holds potential solutions for critical environmental issues, optimizing the photocatalytic efficacy of photochromic substances has not been adequately addressed. This research advances the study of REMOHs, focusing on the properties of gadolinium oxyhydride (GdHO) both theoretically and experimentally. The electronic and structural characteristics of GdHO, vital for ceramic technology, are thoroughly examined. Explicitly determined work functions for GdH2, GdHO, and Gd2O3 stand at 3.4 eV, 3.0 eV, and 4.3 eV, respectively. Bader charge analysis showcases GdHO’s intricate bonding attributes, whereas its electron localization function majorly presents an ionic nature. The charge neutrality level is situated about 0.33 eV below the top valence band, highlighting these materials’ inclination for acceptor-dominant electrical conductivity. Remarkably, this research unveils GdHO films’ photocatalytic capabilities for the first time. Even with their restricted surface due to thinness, these films follow the Langmuir–Hinshelwood degradation kinetics, ensuring total degradation of methylene blue in a day. It was observed that GdHO’s work function diminishes with reduced deposition pressure, and UV exposure further decreases it by 0.2 eV—a change that reverts post-UV exposure. The persistent stability of GdHO films, hinting at feasible recyclability, enhances their potential efficiency, underlining their viability in practical applications. Overall, this study accentuates GdHO’s pivotal role in electronics and photocatalysis, representing a landmark advancement in the domain

Experimental and Theoretical Investigation of Gadolinium Oxyhydride (GdHO) Thin Films : Optical, Photocatalytic, and Electronic Properties

Oxyhydrides of rare-earth metals (REMOHs) exhibit notable photochromic behaviors. Among these, yttrium oxyhydride (YHO) stands out for its impressive transparency and swift UV-responsive color change, positioning it as an optimal material for self-cleaning window applications. Although semiconductor photocatalysis holds potential solutions for critical environmental issues, optimizing the photocatalytic efficacy of photochromic substances has not been adequately addressed. This research advances the study of REMOHs, focusing on the properties of gadolinium oxyhydride (GdHO) both theoretically and experimentally. The electronic and structural characteristics of GdHO, vital for ceramic technology, are thoroughly examined. Explicitly determined work functions for GdH2, GdHO, and Gd2O3 stand at 3.4 eV, 3.0 eV, and 4.3 eV, respectively. Bader charge analysis showcases GdHO’s intricate bonding attributes, whereas its electron localization function majorly presents an ionic nature. The charge neutrality level is situated about 0.33 eV below the top valence band, highlighting these materials’ inclination for acceptor-dominant electrical conductivity. Remarkably, this research unveils GdHO films’ photocatalytic capabilities for the first time. Even with their restricted surface due to thinness, these films follow the Langmuir–Hinshelwood degradation kinetics, ensuring total degradation of methylene blue in a day. It was observed that GdHO’s work function diminishes with reduced deposition pressure, and UV exposure further decreases it by 0.2 eV—a change that reverts post-UV exposure. The persistent stability of GdHO films, hinting at feasible recyclability, enhances their potential efficiency, underlining their viability in practical applications. Overall, this study accentuates GdHO’s pivotal role in electronics and photocatalysis, representing a landmark advancement in the domain

Co-Sputtering Crystal Lattice Selection for Rare Earth Metal-Based Multi Cation and Mixed Anion Photochromic Films

Rare-earth oxyhydride (ReOxHy) films are novel inorganic photochromic materials that have strong potential for applications in windows and optical sensors. Cations greatly influence many material properties and play an important role in the photochromic performance of ReOxHy. Here we propose a strategy for obtaining Gd1−zYzOxHy films (z = 1, 0.7, 0.5, 0.4, 0.35, 0.25, 0.15, 0) using one-step direct-current (DC) magnetron co-sputtering. Distinct from the mixed anion systems, such material would belong to the class of mixed anion and mixed cation materials. For Gd1−zYzOxHy films, different co-doping ratios can help tune the contrast ratio (that is, the difference between coloration and bleaching transmittance) and cycling degradation, which may be related to the lattice constant. X-ray diffraction (XRD) patterns show that the lattice constant increases from 5.38 Å for YOxHy to 5.51 Å, corresponding to Gd0.75Y0.25OxHy. The contrast ratio, in particular, can be enhanced to 37% from 6.3% by increasing the lattice constant, directly controlled by the co-sputtering power. When the lattice constant decreases, the surface morphology of the sample with the smallest lattice constant is essentially unchanged by testing in air with normal oxidation for 100 days, suggesting great improvement in environment durability. However, the crystal structure cannot be overly compressed, and co-sputtering with Cr gives black opaque films without photochromic properties. Moreover, because the atomic mass of different rare earth elements is different, the critical pressure p* (films deposited at p p* remain metallic dihydrides) is different, and the preparation window is enlarged. Our work provides insights into innovative photochromic materials that can help to achieve commercial production and application

Yttrium Oxyhydrides for Photochromic Applications: Correlating Composition and Optical Response

It has been recently demonstrated that yttrium oxyhydride(YHO) films can exhibit reversible photochromic properties when exposed to illumination at ambient conditions. This switchable optical propertyenables their utilization in many technological applications, such as smart windows, sensors, goggles, medical devices, etc. However, how the composition of the films affects their optical properties is not fully clear and therefore demands a straightforward investigation. In this work, the composition of YHO films manufactured by reactive magnetron sputtering under different conditions is deduced in a ternary diagram from Time-of-Flight Elastic Recoil Detection Analysis (ToF-ERDA). The results suggest that stable compounds are formed with a specificchemical formula – YH2-δOδ. In addition, optical and electrical properties of the films are investigated, and a correlation with their compositions is established. The corresponding photochromic response is found in a specific oxygen concentration range (0.45 < δ < 1.5) with maximum and minimum of magnitude on the lower and higher border, respectively

Preferential Orientation of Photochromic Gadolinium Oxyhydrides

We report preferential orientation control in photochromic gadolinium oxyhydride (GdHO) thin films deposited by a two-step process. Gadolinium hydride (GdH2-x) films were grown by reactive magnetron sputtering, followed by oxidation in air. The preferential orientation, grain size, anion concentrations, and photochromic response of the films are strongly dependent on the deposition pressure. GdHO films show preferential orientation along the [100] direction and exhibit photochromism when synthesized at deposition pressures up to 5.8 Pa and. The photochromic contrast is larger than 20 % when the films are deposited below 2.8 Pa with 0.22 H2/Ar flow ratio. We argue that the degree of preferential orientation defines the oxygen concentration which is known to be a key parameter for photochromism in rare-earth oxyhydride thin films. The experimental observations described above are explained by the oxidation-induced decrease of the grain size as a result of the increase of the deposition pressure of the sputtering gas. </p